Anti-sticking composition for frying and baking



June 15, 1965 J. A. M GRORY 1 ANTI-STICXING COMPOSITION FOR FRYING ANDBAKING Filed Jan. 2, 1962 Oxyste a Pin ZNVENE GR Jwa5i my? United StatesPatent 0 3,189,465 ANTl-STTQKENG CGMPGHTHBN FRYHQG AND BAKING James A.McGrory, Cincinnati, Ohio, assignor to The Procter 8: Gamble Company,Qincimati, iihio, a corporation of @hio Filed 32 2, 1.962, Ser. No.163,765 8 (Ilairns. (Cl. 99-4123) This invention relates to compositionswhich prevent food from sticking to the surface of the fryin pan orother utensils used during cooking. More particularly, this inventionrelates to the discovery that certain novel compositions which contain ahydrogenated and oxygenated glyceride oil have outstanding anti-stickingproperties useful for frying, baking, and other cocking purposes.

One of the essential steps in the frying and baking of foods is thegreasing of the cooking surface. A common practice is to coat thecooking vessel with an oily matenial such as a vegetable oil or ananimal fat. It is known that such materials function as efiicientheat-transfer media between the source of the heat and the food to becooked.

Despite their effectiveness as heat transfer media, the oils and fatsnormally employed for frying and baking have several disadvantages. Itis well known that much oil or fatty material is absorbed by the foodduring the cooking process. Moreover, at the temperatures generallyrequired for cooking, the oil and the food are subject to oxidativedeterioration. The combined action of this deterioration and absorptionof oil tends to cause the food to stick to the frying pan or otherutensils used during cooking. The oxidative deterioration and loss ofsurface grease frequently produces smoking and causes undesirableblackened areas to appear on the surface of the food as well as on thecooking surfaces. In addition, the absorption of substantial quantitiesof oil by the food is unsatisfactory from the standpoint of lowfatdieting.

Accordingly, it is an object of this invention to provide a cookingcomposition which substantially prevents food from sticking on utensilsduring frying, balding, and other cooking preparations.

It is another obiect to provide a method of applying a very thin film ofan anti-sticking material between the food and the cooking utensils sothat, in efiect, a substantially greaseless frying or baking may becarried out which is particularly suitable for .people on a low-fatdiet.

it is a further object to provide a cooking surface that remainssubstantially free of carbonized material during the cooking process toallow the preparation of nonbl-ackened fried and baked food products andto facilitate cleaning of the cooking implements.

it is still another object to provide a cooking grease from edibleglyceride oils and fats.

Still a further object is to modify the physical properties of edibleglyceride oils to adapt them to anti-sticking frying and baking uses.

With these objects in view, together with such other objects andadvantages as may subsequently appear, the invention is carried intoefiect by the employment of certain substances and the treatment thereofas hereinafter de scribed and particularly defined in the appendedclaims.

In .the accompanying drawing a tnilinear diagram is shown in which thearea within the lines ABCDA represents the preferred anti-stickingcomposition in combination with a volatile propellant. The ingredientsare shown in percent by weight.

The present invention is based on the discovery that certain fattyglyceride compositions containing substantial amounts of a hydrogenatedand oxygenated glyceride Fetented June '15, 155

oil have outstanding anti-sticking properties and can be applied tocooking utensils in the form of a very thin film either directly or bymeans of aerosol spraying from a pressurized vessel which contains,additionally, a volatile propellant.

In accordance with the broad aspects of the present invention it isessential that the anti-sticking composition contain a base oil that isboth hydrogenated and oxygenated. Moreover, it is essential that thebase oil is first very highly hydrogenated and then slowly oxygenated byheating in a stream of air. The base oil which is processed in the saidmanner can .then be used directly or can be combined with certaindiluent fats and oils to repare anti-sticking compositions which areuseful for frying, baking, and other cooking purposes.

The base oil used is selected from the group of edible glyceri-des ofvegetable, animal, marine, or synthetic origin having fatty chainlengths of about 12 to about 22 carbon atoms. it has been foundpreferable to use an oil that has a high proportion of fatty chainlengths of about 18 carbon atoms such, for example, as cottonseed oil orsoybean oil, although other edible vegetable oils such as corn oil,coconut oil, palm oil, peanut oil, sesame seed oil, sunflower seed oil,and rapeseed oil, and animal fats such as lard and tallow, and marineoils such as whale oil, sardine oil and menhaden oil are also usable.Suitable synthetic oils include glycerides containing one or twoshort-chain fatty acids, or oils prepared by random or low-temperatureinteresterification.

Hydrogenation of the base oils can be carried out by any of theconventional methods and generally consists of a batch process wherebythe oil is contacted with hydrogen in the presence of a nickel catalyst.The addition of hydrogen to the triglyceride molecule converts theunsaturated fatty acid moiety into the corresponding saturated fattyacid. Hydrogenation should be carried out until the hardened oil has aniodine value of less than about 25, although it has been foundparticularly advantageous to hydrogenate to an [iodine value of lessthan 8 and preferably about 6.

After it is hydrogenated, the base oil is then subjected to an oxidationreaction in which it is simultaneously treated with air and heat. Theheating is conducted preferably at temperatures in the range of about200- 250 C. and the air is blown through the oil at a rate of about15-25 cubic feet per minute per 1000 pounds of oil for a period of about5 to 8 hours, preferably until the treated oil attains a butyrorefractive index of about 601-1 at 48 C.

While it is neith r essential to use a treated oil having a refractiveindex as set forth above, nor necessary to conduct the entire oxidationwithin the aforesaid ranges, it has been found that the anti-stickingactivity of the treated oil is optimized if a considerable portion ofthe oxidizing reaction is conducted with the heretofore described amountof heating and air blowing. Thus, the final oxidized oil will not bematerially deprived of its anti-sticking activity if a portion of theoxidation reaction is conducted, for example, at temperatures below 200C. or if some air is blown through the oil, for example, at a rate above25 cubic feet per minute per 1000 pounds of oil. Moreover, therefractive index of the final oil may vary somewhat from the describedlevel depending upon, for example, the length of the hydrocarbon chainin the base oil or on the degree of hydrogenation or saturation of thesaid oil.

At the conclusion of the aforesaid oxidizing step the treated oil iscooled. It can then be blended into a diluent oil or fat to prepare theanti-sticking compositions of this invention.

The oil that has been hydrogenated and oxygenated in the aforesaiddescribed manner is hereinafter referred to as oxystearin because itsubstance with. oxygen introduced into the molecule. The sufiix -stearin(as used herein) embraces not only tristearin, but also mixed glyceridescontaining pahnitic, l stearic, ara chidic, and other saturated fattyacids which comprise the bulk of the solid'glycerides referred to in ceeses is a hardened stearin type the-tradeas stearins. The saidoXy-stearin generally has a dark-brownish solid consistency at roomvtemperature. However, it is to be understood that for the purposes ofthis invention the oxystea rin is not intended to -be limited lbyanyspecific process for itspreparation.

' It has been found that. a composition which contains fromabout %10about 95% and preferably frornabout 20% to about by weight of oxystearinblended-with a complement of a diluent oil or fat displaysremarlgablc Ifrying, baking, and other coolging processes, although the oxystearinmay be applied anti sticking properties during directly to the cooldngutensil without such additional dilution. The diluent can be derivedfrom any edible vegetable oil such as cottonseed oil, soybean oil,coconut oil, palm oil, corn oil", or an edible animal fat such as lardoptallow, or a marine oil such as whale, menhaden, or

sardine oil, or synthetic oils such as those prepared by random or Ilow-temperature interesterification or glycerides containing one or twoshort-chain fatty acids, several of which may be combined in variousproportions.

1 The diluent facilitates the application of the oxy-stearin in the formof a thin film on the cooking utensils.

I 7 Various minor ingredients such as antioxidants and crystallizationinhibitors can be included in the diluent oil without destroying theprimary benefits of the anti-sticking agent.

Although the anti-sticking corn-positions herein defined can beappliedto the cooking utensils with a brush or by other means such as acloth or an absorbent paper towel, they are preferably applied in theform of a fine spray under pressure. In this way, the surfacemay berapidly and uniformly covered with avery thin film: The thin filmisnecessary not only from the standpointof low-fat I dieting but alsoservesto conceal the heretofore disclosed brownish color of theoxysteanin. In order' to coat the 'cookingsurface with such a-film it ispreferable that the composition be admixed with a suitable aerosolpropellant so that it can be expelled from a pressurized can or. othervessel.- 'Any' propellant which is highly volatile at ordinarytemperatures and pressures can be used, but. it is preferable that thepropellant be non-toxic, odorless, tasteless and stable.

'For the purpose of this invention, various fiuoro-halo derivatives oflow molecular weight hydrocarbons such,

; for example, as trichloromonofiuoromethane, dichlorodifluoromethane;andmixtures thereof have been found to be satisfactory propellants.Other fluorocarbons such, for example, as octafiuorocyclobutane andcompressed gases such, for example, as nitrous oxide, carbondioxide,'nitrogen, andgother. propellants which are highly volatile at Lordinary temperatures and pressures, either alone'or in combination withthe aforesaid substances can be used i with comparable results.

" solved in the-volatile propellant.

The mixture to be sprayed can contain from about 0.1% to about 40% byweight of the aforesaid oxystearin disstearin-containing glycerideblends are also preferably dis i solved in the volatile propellant'sothat theingredientsof i the pressurized composition are distributed inthefollow- -Oxystearin r7 0.140 f Diluentglyeerides j V 0.005-48Volatile propellant 40-99.89 5

ing proportions:

Percent by weight The. said preferred aerosol composition lies withinthe L lines ABCDAof the trilinear diagram of thedrawing.

The following. examples are illustrative ofthe present invention, but itwill be understood that the invention is not limited thereto.

The aforesaid oxycaloric frying purposes.

cooked for one minute.

/ EXAMPLE 1 The following Table I records the results obtained with aseveral substances which were used as anti-sticking agents during thefrying ofeggs. The substance to be used in each instance was initiallyapplied in excess to the inner surface of a slightly warm'electricfryingpan. -As.the

temperature of the pan increased somewhat, the excess 'oily material waspoured out and blotted off With'an absorbent paper towel so that barelya tbin'film remained on the surface of the pan. Eggs were then fried inthe pan at a temperature of 320 F. andtheir tendency to stick to thesurface was observed.

1 Consisting primarily of hydrogenated soybean oil. (1V. -75) and minoramounts of hardstocl: and monoglyceridc emulsifiers.

T he ox stearin in this exam 1e was Jre ared from h drogenatedcottonseed oil having an iodine value of. about 6. to '8 and a butyrorefractive index of about 391-1 at 7 48 C. The said iydrogenated oil wasbodied with heat at about225 250 C. and air blown at the rate of about20 cubic feet; per minute per 1000pounds of oil until the final productmet the following specifications:

Acid number 14. Iodine value 14., Saponification number 225-340.Hydroxyl value 3 0415. Unsaponifiable matter 0.8%. i Butyr-o refractiveindex 60:1 at 48 C. Molecular weight -4 925-975.

The oxystearin was a dark chocolate-brown colored material having agreay-wax consistency at room. temperature and a texture similar torefrigerated butter.

When a composition consisting of 20% by weight. of oxystearin preparedfrom rapeseed base oil hydrogenated to an iodine value of about 8andblended with by weight of refined rapeseed diluent'oil is substitutedfor. the blend of-oxystea rin and cottonseed oil shown above,

substantially the same results are obtained. 'H0WVl,' when theproportion of oxystearin in the glyceride oil blend is reduced to lessthan about 20%, the anti-sticking effects are notpronounced, and aheavier application of amore dilute oXystearin-con-taining oilymaterialvresults in a film that is too thick for substantiallygre-aseless low- EXAMPLE 2 The following Table II recordsthe resultsobtained with several substances Which-were usedas anti-sticking agentsduring the cook ng of oatmeal. The substanceto be used in. eachinstance; was applied in the formof a thin film to :the inner surface ofav standard commercial enameled pan. The pan was provided.;with water.(in'a 2:1 proportion of water to oats) and a little salt, and broughtto a boil. Quick Oatswere then stirred'in and Serving portions ofoatmeal were removed and the pan was allowed to cool fora normal eatinginterval. Then the pans were cleaned and a judgment was'made of thesticking effect and of the ease ordifiicultyofcleaning the innersurface. i

The heat was removed and 'the, pan was covered and allowed to, rest forfive" minutes.

Table II Plain oatmeal pan with no coating Hydrogenated vegetable oilshortening Oxystearin Z 1 Consisting primarily of hydrogenated soybeanoil (LV. 70-75) and minor amounts of hardstoek and monoglycerideemulsifiers.

2 Prepared as in Example 1 above.

EXAMPLE 3 The following Table III records the results obtained withseveral substances which'were used as anti-sticking agents during thebaking of blueberry mufiins. The substance to be used in each instancewas applied in the form of a thin film to the inner surface of standardmufiin pans. A batter was prepared from a standard comme cial blueberrymuffin mix and placed in the pans to a lz-cup depth. The muiiins werebaked for -25 minutes in an oven heated to 400 F. The muffins wereallowed to cool 10-15 minutes and then removed from the pans. Theirtendency to stick to the surface of the pan and the ease or difiicultyof removal therefrom was observed.

Table III Substance Tested Sticking Efiects Severe sticking.Aplpgrecieble sticking.

ND sticking. virgrally no sticking.

1 Consisting primarily of hydrogenated soybean oil (LV. 70-75) and minoramounts of hardstock and monoglyceride emulsifiers.

2 Prepared as in Example 1 above.

When a composition consisting of 95% by weight of oxystearin preparedfrom coconut base oil hydrogenated to an iodine value or" about 8 andblended with 5% by weight of refined coconut diluent oil is substitutedfor the blend of oxystearin and cottonseed oil shown above,substantially the same results are obtained. However, as the proportionof oxystearin in the glyceride oil blends is increased to levels greaterthan about 40% by weight, it becomes more difiicult to apply theanti-sticking material to the surface of the pan in the form of a verythin film. Thus, it is preferable to use not more than about 40%oxystearin in the oil blend.

EXAMPLE 4 Table IV Composition Tested Frying Effects oxystearin and 70%propellant No sticking; ven distribution of a very thin film.

Moderate sticking; uneven distribution of an oily film (streamingefiect).

60% oxystearin and propellant When an aerosol composition consisting of40% by weight of oxystearin and by Weight of propellant d is substitutedfor the 30:70 mixture shown above, substantially the same results areobtained. However, when the proportion of oxy-stearin is increased togreater than about 40% by weight, dispersion in the propellant becomesexceedingly difiicult and undesirable streaming effects are producedduring the aerosol spraying.

EXAMPLE 5 20 parts by weight of oxystearin, prepared in accordance withExample 1, above, were thoroughly blended with parts by weight ofcottonseed oil. This blend was then mixed with a volatile propellant,which consisted of a 35:65 mixture of dichlorodifiuoromethane andtrichloromonofiuoromethane, and packed under pressure in an aerosolcontainer. The final pressurized composition was then sprayed onto theinner surface of a frying pan in the form of a fine spray. The followingTable V records the anti-sticking effects observed with variousproportions of propellant and the 20:80 blend of oxystea-rin andcottonseed oil when sprayed for diderent lengths of time onto a fryingpan in which eggs were then tried at temperatures of about 320 F.

Table V Spraying Time,

Sticking Effects o. 60 No sticking. 5 Appreciable sticking.

10 Do. 20 No sticking. 60 D0.

For most frying purposes it is desirable to spray the aerosolcomposition onto a standard size home frying pan in less than about 20seconds and preferably in several seconds. A longer spraying periodwould tend to deplete the contents of the aerosol container too rapid-1y. It is also important to prepare the anti-sticking composition in amanner so that a spraying time of more than a few seconds will notproduce too thick of a film of oily material on the frying pan. A thickfilm would be unsatisfactory for purposes of low-fat dieting and wouldtend to show the heretofore disclosed brownish color of the oxystearin.It has been found that the aforesaid objectives can be attained withoutstanding satisfaction with an aerosol composition which lies withinthe lines ABCDA of the trilinear diagram of the drawing.

Although the compositions of this invention are eminently suitable foranti-sticking purposes during various cooking processes, they can beused in other applications where an o-leaginous coating is desired,particularly where resistance to oxidative deterioration is important.

What is claimed is:

1. The method of improving a cooking utensil for frying and baking whichComprises coating the cooking surface of the said utensil with a thinfilm of an anti-sticking composition consisting esssentially of fromabout 20% to about by weight, oxystearin and from about 5% to about 80%,by weight, diluent glyceride.

2. The method of improving a cooking utensil for frying and baking whichcomprises coating the cooking surface of the said utensil with a thinfilm of an antisticking composition consisting essentially of from about20% to about 40%, by weight, oxystearin and from about 60% to about 80%,by weight, diluent glyceride.

3. The method of improving a cooking utensil for frying and baking whichcomprises coating the cooking surface of the said utensil by sprayingsaid surface with an antisticking composition consisting essentially offrom about mixed with vfrom about 60% to about 99.9%, by weight,non-toxic volatile propellant:

and'baking which comprises coating the cooking surface ,of thesaid'utensil'by spraying'said surface with ananti sticking jcompositionconsisting essentially of from about to about 95%, by weightfoxystearinand from about to about '80%,"by weight,"diiuent "glyceride, saidanti-sticking con'ipos'itio'n beingthordu'ghlji 'mixed 'with' anon-toxic yolatiie propeilant, and 'said'ingredients being distributedin proportions withinthe lines ABCDA .of the triiine'ar diagram of thedrawing. 7

agent on cooking utensils consisting essentially of from about 20% toabout 95%, by weight',oxystearin and from about 20% to about 40%, byweight, ox'ysteafin and from; about to about by weight, diluent'glyceride.

a pressurized container formse as an anti-sticking agent by Weight,oxystearin thoroughly mixed with from about 60% to about 99.9% byweight, non-toxic volatile propeliant.

5. A cooking conposition for use as an anti stickingconsistingessentially of from about 0.1% to about 40%,

0,1%"to about 40%, by weight, oxystearin thoroughly 4. The method ofimproving a cooking utensil for frying about 5% to about 80%, by weight,diluent glyceride. v

6. A cooking-composition for'use as an anti-sticking I agent on cookingutensils consisting essentia'llyfof from 20" 7. A cooking compositionadapted to be dispensed from I 8; A cookingcompositionadaptedtobedis'pensed'frdinf" by weight, diluent glyceride, said cooking con oosition V fbeing thoroughlywith' a non-tonic yollatilepropella'iig'andsaid ingredients being distributed inproportio'ns 7within the lines ABCDA of the trilinear diagram'ot the drawing.

' References Cited by the Examiner W ToB'IAsEi 'LEVOW, ABRAHAM WINKELsrn N,

, V Examiners.

1. THE METHOD OF IMPROVING A COOKING UNTENSIL FOR FRYING AND BAKINGWHICH COMPRISES COATING THE COOKING SURFACE OF THE SAID UTENSIL WITH ATHIN FILM OF AN ANTI-STICKING COMPOSITION CONSISTING ESSENTIALLY OF FROMABOUT 20% TO ABOUT 95%, BY WEIGHT, OXYSTEARIN AND FROM ABOUT 5% TO ABOUT80%, BY WEIGHT, DILUENT GLYCERIDE.